EP1597294A1 - Copolymeres phenol uree/melamine formaldehyde, leur procede de production et leur utilisation - Google Patents

Copolymeres phenol uree/melamine formaldehyde, leur procede de production et leur utilisation

Info

Publication number
EP1597294A1
EP1597294A1 EP04715250A EP04715250A EP1597294A1 EP 1597294 A1 EP1597294 A1 EP 1597294A1 EP 04715250 A EP04715250 A EP 04715250A EP 04715250 A EP04715250 A EP 04715250A EP 1597294 A1 EP1597294 A1 EP 1597294A1
Authority
EP
European Patent Office
Prior art keywords
copolymer according
urea
formaldehyde
condensation
phenol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP04715250A
Other languages
German (de)
English (en)
Inventor
Kerstin Schmidt
Dirk Grunwald
Helmut Miertzsch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Original Assignee
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV filed Critical Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Publication of EP1597294A1 publication Critical patent/EP1597294A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
    • C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
    • C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
    • C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
    • C08G14/10—Melamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
    • C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
    • C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
    • C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
    • C08G14/08—Ureas; Thioureas

Definitions

  • the invention relates to phenol-urea / melamine-formaldehyde copolymers, a process for their preparation and the use of these copolymers.
  • the copolymers or polycondensation resins according to the invention are preferably used for the production of wood materials or further processing of wood or wood materials.
  • thermosetting adhesives that are obtained via polycondensation
  • two important connection classes can be distinguished:
  • aminoplastic adhesives such as urea-formaldehyde adhesives (hereinafter
  • the phenolic materials such as phenol-formaldehyde adhesives (hereinafter
  • PF adhesives phenol-resorcinol-formaldehyde adhesives
  • PRF adhesives phenol-resorcinol-formaldehyde adhesives
  • connection classes especially in the wood and wood-based materials sector, are outstanding Importance. With the help of these adhesives, a wide variety of materials can be bonded together.
  • the most important representative of the aminoplastic adhesives are the UF adhesives and the most important representative of the phenolic adhesives are the PF adhesives.
  • UF adhesives are manufactured using a three-step synthesis process.
  • a low molecular weight precondensate is produced from the components formaldehyde and urea under alkaline conditions (pH 8-10) at temperatures between 50 ° C and 90 ° C in a discontinuous stirred reactor.
  • Various akali and alkaline earth metal hydroxides (NaOH, KOH, Ca (OH) 2 ) or amines can be used as catalysts.
  • the molar ratio of urea-formaldehyde is between 1: 1.8 and 1: 2.2. Depending on the conditions, this phase primarily forms mono-, di- and trimethylol urea and other low molecular weight methylol ureas.
  • this methylolation is not separated from the subsequent condensation by the pH but by the temperature.
  • methylolation occurs, which passes seamlessly into the condensation as the temperature increases further.
  • the optimum reaction for the condensation is around 90 ° C. The reaction is stopped depending on the water compatibility or the viscosity by lowering the temperature.
  • the PF adhesives are usually manufactured industrially discontinuously (i.e. in batches).
  • PF adhesives have the disadvantages of a dark color (ie a disruptive optical impression), are relatively expensive and have a low reactivity compared to UF adhesives.
  • the alkali content of the PF adhesives further complicates the subsequent coating (for example with acid-curing melamine resin soaking films).
  • the alkali content of the PF adhesives also has the disadvantage that when these PF adhesives are used in wood-based panels, the leveling moisture of the panel is increased, which also increases the risk of biological damage to the wood-based panel
  • the UF adhesives are characterized by a light, almost transparent color, so that the adhesive joint is not visually recognizable in most applications. They are still cheaper than PF adhesives and have a relatively high reactivity. However, they have the disadvantage of low hydrolitic stability and associated formaldehyde emissions.
  • PUF adhesives phenol-urea-formaldehyde adhesives
  • the present invention is therefore based on the object of overcoming the disadvantages of the prior art and of providing a copolymer of urea, formaldehyde and phenol in which all monomers are incorporated as completely as possible into the adhesive matrix.
  • the copolymer according to the invention can be obtained by condensation of an aqueous precondensate made from phenol and / or phenol derivatives (hereinafter referred to as PF precondensate) with an aqueous precondensate made from urea and / or urea derivatives and / or melamine and / or melamine derivatives (hereinafter referred to as UF or MF or MUF precondensate) and formaldehyde or a formaldehyde derivative in the presence of an immobilized catalyst which contains a matrix which can give off H + ions, and an immobilized catalyst which contains a matrix which can give off OH " ions or one immobilized catalyst which contains a matrix which can give off OH " ions and H + ions.
  • PF precondensate an aqueous precondensate made from phenol and / or phenol derivatives
  • UF or MF or MUF precondensate aqueous precondens
  • a mixture of an anionic ion exchanger and a cationic ion exchanger is preferred as the immobilized catalyst, but other (immobilized) substances (for example zeolites) or biomolecules which can give off OH ' ions or H + ions are also suitable.
  • immobilized substances for example zeolites
  • biomolecules which can give off OH ' ions or H + ions are also suitable.
  • urea or urea derivative and phenol or phenol derivative are reacted with formaldehyde in separate reactions in the first step. The reaction is controlled by time, pH and temperature so that only methylol ureas or methylol phenols are formed.
  • the immobilized catalyst is preferably used catalytically.
  • the condensation is carried out by setting a suitable reaction temperature and reaction time.
  • the so-called post-condensation can be carried out.
  • the important product properties such as viscosity, solids content, reactivity and storage stability are set.
  • copolymers according to the invention contain no detectable or only small amounts of monomers. This can be demonstrated by gel permeation chromatography (GPC) and NMR spectroscopy ( 13 C-NMR).
  • the copolymers according to the invention therefore have the advantage that no or only small amounts of latent acids as anions (for example formates, acetates or hydrogen phosphates) or no or only small amounts of alkali are contained in the adhesive or in a hardened adhesive joint.
  • latent acids as anions for example formates, acetates or hydrogen phosphates
  • alkali residues increase the equilibrium moisture content of a wood-based panel.
  • the copolymers according to the invention have the advantage that regeneration of the catalyst is possible.
  • the catalyst used in the condensation of the precondensates is heterogeneous and can therefore be separated from the reaction mixture which is moving past this immobilized catalyst.
  • it is also sufficient to use only small amounts of catalyst, which further improves the sensitivity of the adhesives to hydrolysis.
  • the use of the immobilized catalysts makes it easier to control the polycondensation.
  • the condensation takes place with the release of energy (it is an exothermic reaction). Heat is released, which further accelerates the reaction. Effective control and cooling devices are therefore necessary in the manufacture of UF and PF adhesives.
  • These reactions to produce UF or PF adhesives are very difficult to control, but can be controlled by adding additional alkaline or acidic catalysts. However, this has the disadvantage of additional acidic or basic components in the resulting polycondensation resins. In the process according to the invention, this problem cannot occur due to the use of the immobilized catalysts, so that an uncontrolled increase in the reaction temperature can be ruled out and nevertheless no undesired acid or base residues remain in the polycondensation resin obtained.
  • the phenol or phenol derivatives are preferably selected from the following compounds for producing the PF precondensate: unsubstituted phenol, substituted with linear or branched alkyl groups Phenol derivatives (in particular o-, m-, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-tert-nonylphenol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2 , 6-dimethylphenol or 3,5-dimethylphenol), compounds which contain several phenol units (especially bisphenol A and bisphenol F), resorcinol and resorcinol dehvates, pyrolysis oils, tannins, lignins and cashew nut shell liquid (CNSL).
  • Phenol derivatives in particular o-, m-, p-cresol, p-tert-butylphenol, p-tert-octyl
  • Unsubstituted phenol and mixtures which contain more than 95 mol% of unsubstituted phenol are particularly preferred.
  • the urea or the urea derivative used in the preparation of the UF or MUF precondensate is preferably selected from the following compounds: unsubstituted urea, derivatives of urea which contain alcohol groups (in particular monomethylol urea and dimethylol urea), urea derivatives substituted by alkyl groups (in particular methyl urea) , Unsubstituted urea is particularly preferred.
  • the melamine or the melamine derivative used in the production of the MF or MUF precondensate is preferably selected from the following compounds: unsubstituted melamine and salts of melamine (in particular acetates, formates, lactates and oxalates). Unsubstituted melamine is particularly preferred.
  • Preferred uses of the copolymers according to the invention exist in the manufacture or further processing of wood or wood-based materials (e.g. wood fiber boards and chipboard), in particular as an adhesive, binder, glue or foundry aid.
  • wood or wood-based materials e.g. wood fiber boards and chipboard
  • the phenol-urea-formaldehyde copolymers or phenol-melamine-formaldehyde copolymers according to the invention are obtained by condensation a) of an aqueous precondensate composed of phenol and / or one or more
  • Step d) can be omitted completely for the production of impregnating resins.
  • the PF, UF, MF and MUF precondensates are preferably produced in such a way that no or only a few oligomers (preferably less than 10% by weight, particularly preferably less than 5% by weight) are present, ie the precondensates are apart from these oligomers consists only of methylolated monomers (especially mono-, di- and trimethylol urea, mono-, di- and trimethylolphenol, mono-, di- and trimethylolmelamine or single to triple methylolated derivatives of these compounds).
  • the reaction to produce the precondensates is therefore preferably carried out in aqueous solution at pH values between 5 and 9.
  • the PF precondensates are particularly preferably produced at pH values between 7 and 9, very particularly preferably at pH 8.
  • a reaction temperature between 15 ° C. and 90 ° C. particularly preferably room temperature (approx. 20-25 ° C.)
  • the UF, MF and MUF precondensates are produced particularly preferably at pH values between 5 and 7, very particularly preferably at pH 6.
  • UF precondensate 60.6 g (1 mol) of urea are added to 162.3 ml (2 mol) of formaldehyde solution (37%). The reaction mixture is heated to 40 ° C for 2min and then cooled to RT.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Phenolic Resins Or Amino Resins (AREA)

Abstract

L'invention concerne des copolymères phénol urée/mélamine formaldéhyde que l'on obtient par condensation d'un précondensat aqueux constitué de phénol et/ou de dérivés phénolés avec un précondensat aqueux constitué d'urée, de dérivés d'urée, de mélamine et/ou de dérivés de mélamine et de formaldéhyde en présence d'un échangeur d'ions anionique et d'un échangeur d'ions cationique. Dans la première étape, l'urée et le phénol sont transformés dans des réactions distinctes avec le formaldéhyde. La réaction est commandée par le temps, la valeur du pH et la température de façon à former uniquement des urées méthylol ou des phénols méthylol. A l'étape suivante, les deux charges de départ réactionnelles sont combinées et sont mises en contact avec l'échangeur d'ions immobilisé (qui peut également être utilisé de manière catalytique).
EP04715250A 2003-02-28 2004-02-27 Copolymeres phenol uree/melamine formaldehyde, leur procede de production et leur utilisation Withdrawn EP1597294A1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE10308792 2003-02-28
DE10308792 2003-02-28
DE10318365 2003-04-23
DE10318365 2003-04-23
PCT/DE2004/000372 WO2004076514A1 (fr) 2003-02-28 2004-02-27 Copolymeres phenol uree/melamine formaldehyde, leur procede de production et leur utilisation

Publications (1)

Publication Number Publication Date
EP1597294A1 true EP1597294A1 (fr) 2005-11-23

Family

ID=32928847

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04715250A Withdrawn EP1597294A1 (fr) 2003-02-28 2004-02-27 Copolymeres phenol uree/melamine formaldehyde, leur procede de production et leur utilisation

Country Status (4)

Country Link
US (1) US20060100412A1 (fr)
EP (1) EP1597294A1 (fr)
DE (1) DE112004000806D2 (fr)
WO (1) WO2004076514A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101576819B1 (ko) 2011-02-17 2015-12-11 포세코 인터내셔널 리미티드 피더 요소와, 이를 포함하는 피더 시스템

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US20060094853A1 (en) * 2004-11-02 2006-05-04 Hexion Specialty Chemicals, Inc. Modified phenol-formaldehyde resole resins, methods of manufacture, methods of use, and articles formed therefrom
DE102004062456A1 (de) * 2004-12-20 2006-06-29 Basf Ag Bindemittel für die Herstellung von Werkstoffen
US8691340B2 (en) 2008-12-31 2014-04-08 Apinee, Inc. Preservation of wood, compositions and methods thereof
US9878464B1 (en) 2011-06-30 2018-01-30 Apinee, Inc. Preservation of cellulosic materials, compositions and methods thereof
RS64897B1 (sr) * 2011-10-21 2023-12-29 Lignum Tech Ag Laminatni panel bez podložnog papira
RU2534550C1 (ru) * 2013-04-25 2014-11-27 Вячеслав Ефимович Цветков Способ изготовления карбамидоформальдегидного олигомера

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101576819B1 (ko) 2011-02-17 2015-12-11 포세코 인터내셔널 리미티드 피더 요소와, 이를 포함하는 피더 시스템

Also Published As

Publication number Publication date
WO2004076514A1 (fr) 2004-09-10
US20060100412A1 (en) 2006-05-11
DE112004000806D2 (de) 2006-01-19

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